Process of manufacturing naphthenates



Patented Oct. 12, 1937 2,095,508

UNITED STATES PATENT OFFICE.

PROCESS OF MANUFACTURING NAPH- THENATES Friedrich Meidert, Frankfort-on-the-Main- Griesheim, Germany, assignor to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-onthe-Main, Germany N Drawing. Application February 23, 1932, Se-

rial No. 594,737. In Germany March 2, 1931 Claims. (Cl. 134-57) This invention relates to a process for produc- 140 C., until the water is completely removed. ing naphthenic acid salts and more particularly The molten naphthenate, thus purified, may be those of the earth metals, the metallic elements directly run into suitable containers from the of the rare earths and of the acid-forming earth producing vessel.

5 metals. Preferably, soluble salts of the metals in ques- 5 When precipitating at ordinary temperatures tion, such as chlorides, sulfates, nitrates, acetates soaps derived from naphthenic acids with soluand so on, are employed as precipitants for the tions of metal salts, the precipitates obtained are naphthenate solution. in a pasty and sticky condition, so that it is very Furthermore, I have ascertained that it is very 0 difficult and all but impossible to wash them out dvantageous, esp y w n Working p p in thoroughly at ordinary temperatures either beucts having a softening point higher than 130 fore or after separation of the mother liquor into 140 C. or melting at these temperatures rather asmuch as rather considerable amounts of the wly, such as, for instance, aluminum nap alkali metal salts formed are left behind in the thenate, to add to the naphthenates duri precipitate, whereby the value of the naphtheafter the precipitation or after melting a liquid 15 nates and their percentage contents of active sicor an easily meltable product, in order to facilicative metals are greatly impaired and the vartate the melting of the p e a and t0 nishes and lacquers produced therewith are unv d ec position. As Such mediums, generfavorably influenced. Moreover, it is very diffially such compounds a su ta w h y d in cult to separate the precipitated naphthenates y atio a hO e US mass With a p t 20 from the mother liquor by suction on an indusnate melting at a low temperature. Especially trial scale, the filter pores being easily clogged ted are, r instance, t drying and m up by the toughish products of precipitation. drying oils, such as linseed oil or linseed oil acids,

When drying the naphthenates in a drying soy bean oil or soy bean oil acids, however, likechamber as usually done, at about 40 0,, much wise the non-drying oils, such as castor oil or its 25 time and labor is necessary so that a drying operacids, and such compounds as liquid triaryl phosation becomes very expensive, and besides it is p s su h as t r sy ph p at y xan n only imperfect as, at the temperature indicated, a and Other products known as Softening agents in superficial incrustation takes place, whereby the the industry dealing With e u c u e o further evaporation of the occluded water is renplastic es. In e following claims y the 30 dered difficult or even impossible; this water conterm plasticizers t ere are to be Understood all tent, moreover, likewise impairs the treatment of these Substances Which facilitate the melting of the naphthenates in question in the manufacture the naphthenates; t e m pr ses both the of varnishes and lacquers, additional substances which at ordinary tem- Now I have found that these drawbacks in the u e e u d a d ose which at o di y 35 manufacture of naphthenates 0f the earth metals p ure are Solid- (aluminium), the rare earth metals (cerium, zir- The removal f w t f m the nap t enat oonium, lanthanum and similar metals), and the may be accelerated during the melting p rat acid-forming earth metals (such as vanadium) by application of a Veellllmy Shortening t e can easily be avoided and the difficulty of the m for drying and by k pi w y he atmos- 40 washing out operation can be completely overp i n, light-colored pr u ts a obcome by carrying out the steps consisting in the tained. The evaporation of the water in a vacuneutralization of the naphthenic acid (commonly 11m y be further accelerated y adding to the called saponification), in the precipitation and hephthehete easily evap Organic in washing the precipitamd product, while mainpounds, such as benzene, xylol, white spirit or 5 taining the liquid in the boiling state. By this other compounds forming with water an azeomeans the alkali metal salts formed by double tropic mixture. decomposition, are retained in the solution and The preparation of the aforementioned naphmay be completely removed by, for instance, three thenates is thus considerably simplified by the washing operations. present process and the drying is effected far 50 After the water employed in the final wash has more rapidly than otherwise. The obtained been withdrawn, the desiccation and drying may products are far superior as regards their purity be carried out in the same reaction vessel withand quality to those obtained by other processes out any difliculty by maintaining the washed and are much more suitable for use in the manuproduct in a molten state, generally at to iacture of lacquers and varnishes. 55

' of naphthenic acid or and'resinates- I 1 1 1 1 I 11 l 1 I I In an analogous mannen: mixed naphthenates: f heavy: metals and earth metals, rare earth metals and acid-forming earth metals, may be 1 prepared in a single step; of working. 1" I 1 1 I 1 invention ,.the parts being by Weight:# I j 1 1 ExampZe-1 '.-.--1000 parts of i crude or purified naphthenic acid are saponified fwhile boiling and stirring with a solution of 290' to '210' parts of 1 caustic soda in accordance: withthe acid number of the naphthem'c acid; The clear Is'oap solution :is quantitatively precipitated with a solution of 1 about 320 .to' r 330 :parts io'i. vanadyl 1I sulfate (VO)SO4I'2H2O. 1 The precipitate formed J is: I washed three times with h'ot'water and. after with' I drawal of the final wash it1iS heated inthe procipitating vat toabout 136 to about 140? C. untilthe adhering water is completely evaporated. I I Then the melt-is directly run; into suitable cone 1 i 1 i I 1 1 Example 2.-1000 parts of crude or purified 1 I naphthcnic acid aresaponified according I1 to its I1 acid number-with :asolution of 260 to 230 parts I of anhydrous sodiumcarbonate, while stirring at 1 boiling temperature; and the clear soap solutionobtained is quantitatively precipitated with a -so-:- lution' of '56il'to. 580 parts of alun'iinum 1chloride.11 I i =When finishingtheprecipitation, 200 parts. of. linseed oil are added; the precipitatedaluminum= naphthenate admixed with linseed'oil is three 1 1 'timesiwashed 'wi th water while stirring, and fir V nally-freed from water after withdrawal ofthe The 'naphthena'tes of aluminum, the rare 1 earths and the acid-forming I earth metals are suitable I as I oil-thickening agents and sizing agents. Furthermore, they, may be used as as-- sistants in the manufacture of isiccatives; the 1 action of which may be essentially. enhanced; in this case, they may be used. either together with 1 I ithe heavy metal and alkaline earth metal salts. together with linoleates i The following examples serve. to illustrate tainera I 1 I 1 final wash by melting it for a short time at 130 to 140 G. Then it is directly run into a suitable container.

Example 3.-1000 parts of naphthenic acid are saponified according to Example 1 or 2, the clear soap solution first is mixed with a solution of 3 10 to 320 parts of cobaltous sulfate, C0804 7H2O, then parts of soy bean oil fatty acids are added, thereupon the remaining naphthenic soap is quantitatively precipitated with a 1 solution of 2010 to 210'parts of cerous chloride, CeCla. The precipitation finished, 75 parts of castor oil are introduced and the precipitate is washed as men- I tioned above. After withdrawal of the final wash, the cobalt-cerium naphthenate with the admixed oil and fattyacids is melted at to C., the adhering wateris evaporated and a completely homogeneous melt of low viscosity is formed. v 1 1 Example 4.--1000 parts of naphthenic acid are saponified as indicated in Example 1 or 2, the clear soap solution is quantitatively precipitated with a solution of i8 0 to 490 parts of zirconium oxychloride, (ZrO)Cl2-8H.2O, and the precipitate formed is washed with water as mentioned in the foregoing examples. After withdrawal of the final wash, 50 parts of toluol are addedand the zirconium naphthenate is freed from water by heating it under reduced pressure.

ln the foregoing examples the saponifica-tion 1 1 .1

of the naphthenic acid may be carried outwith a i corresponding potassium compound.1 V WhatI claim-1 1 1 'ous solutions of alkalimetal naphthenates the im- In the processof producing acomposition. 1 of: matter for drierscontainingnaphthenates of 1 1 1 .1

thegroup consisting of aluminium, cerium zire I I 'conium, lanthanum and vanadiumby precipitat-1- 1 ing said naphthenatesby the interaction of; aque-- 1 I bus-solutions of salts-0f said 'metals withaqueprovement which comprises Washingthe precipi-., 1 I Q i vaporized. 1

'ous' solutions of saltsiof said "metals withpaquecipitated naphthenate with water at boiling temtated naphthenate with :water at boiling tem- I I I perature and drying the washed precipitate, I 1

admixed with a .plasticizer, while maintaining it in a molten state until the: water is completely.

' l '2. Inthe' process of; producing a composition I 1 of matter fordriers containing-naphthenates of I I the group consisting of aluminiumyceriumzir conium;'lanthanum and; vanadiumby precipitating said naphthenates by the interaction ofgaque+ I one I solutions of alkali metal naphthenates' the i I i improvement which comp-rises washing the pre-:

perature and drying thewashed: precipitate. ad--.,

a molten state under reduced pressure,-

1 water is completely :vaporizedl I 1 I 1 1 1 1 I temperature of about 130 C. to about 140 C.

until the water is completely vaporized.

4. In the process of producing a compositionof matter for driers containing naphthenates of the group consisting of aluminium, cerium, zirconium, lanthanum and vanadium by precipitating said naphthenates by the interaction 01' aqueous solutions of salts or said metals with aqueous solutions of alkali metal naphthenates the improvement which comprises washing the precipitated naphthenate with water at boiling temperatureand drying the washed precipitate, admixed with a plasticizer, while maintainingit in a molten state until the water is completely'vaporized, the precipitating, washing and drying operations being carried out in the same vessel. 5. In the process of producing a composition of matter for driers containing aluminium naphthenate by precipitating aluminium naphthenate 1 by the interaction of aqueous solutions of an aluminium salt with aqueous solutions of alkali metal naphthenates theimprovement which comprises washing the precipitated aluminium naphthenate with waterat boiling temperature and drying the washedprecipitate, admixed with a plasticizer while maintaining it in a molten state until the water is completely vaporized.

FRIEDRICH MEIDERT.

mixed with a plasticizer,- whileinaintaining it'in; I I

until the -1.

: 3. In the process I of producing a composition I i I 1 of matter for driers containing naphthenates I of the gro-up consisting of aluminium, cerium, zir-' .1 I I I conium; lanthanum' and vanadium by precip- 1 I I 1 itating said na'phthenates bythe interaction of I aqueous solutions j ofxsalts of said metals with .1 I 1 1 aqueous solutions of alkali 1metalnaphthenates I 1 1 1 'thelimprovement: which comprises washing the 1 precipitated.- naphtlrenate' -with WaterQatTboiling I I I temperature and I drying the :Washed precipitate; I admixed with a plasticizer; by heating itto a 1 1 

